Flavoring compositions and processes utilizing alpha-ketothiols

ABSTRACT

The use of certain Alpha -Ketothiols of the formula   WHEREIN R1 is methyl or ethyl and R2 and R3 are hydrogen, methyl or ethyl to alter the meat flavor and aroma of foodstuffs.

United States Patent [191 Katz et al.

[ FLAVORING COMPOSITIONS AND PROCESSES UTILIZING v ALPHA-KETOTIIIOLS[75] Inventors: Ira Katz, Elberon; William J. Evers,

Atlantic Highlands; Anne Sanderson, Highlands, all of NJ.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

[22] Filed: July 12, 1971 [21] Appl. No.: 162,008

[52] US. Cl 426/65, 260/593 R, 426/364, 426/175 [51] Int. Cl A231 1/26[58] Field of Search 99/140 R; 260/593 R NOV. 20, 1973 OTHERPUBLICATIONS Asinger et a1. Chemical Abstracts 6l:l859(d) (1964).

Primary ExaminerMorris O. Wolk Assistant Examiner-Sidney MarantzAttorney-Lorimer P. Brooks et al.

[57 ABSTRACT The use of certain a-Ketothiols of the formula wherein R ismethyl or ethyl and R and R are hydrogen, methyl or ethyl to alter themeat flavor and aroma of foodstuffs.

8 Claims, No Drawings FLAVORING COMPOSITIONS AND PROCESSES UTILlZlNGALPHA-KETOTHIOLS This invention concerns the use of certain a-ketothiolsto alter the flavor and aroma of foodstuffs.

The term foodstuff as used herein includes both solid and liquidingestible materials for man or animals, which materials usually do, butneed not, have nutritional value. Thus, foodstuffs include meats,gravies, soups, convenience foods, malt and other alcoholic ornon-alcoholic beverages, milk and dairy products, nut butters such aspeanut butter and other spreads, seafoods, including fish, crustaceans,molluscs, and the like, candies, breakfast foods, baked goods,vegetables, cereals, soft drinks, snack foods, dog and eat foods, otherveterinary products, and the like.

The term alter" in its various forms will be understood herein to meanthe supplying or imparting a flavor character or note to an otherwisebland, relatively tasteless substance, or augmenting an existing flavorcharacteristic where the natural flavor is deficient in some regard, orsupplementing the existing flavor impression to modify organolepticcharacter.

There is a continuing search for compositions which can vary, fortify,modify, enhance or otherwise improve (i.e. alter) the flavor and aromaofa foodstuff. To be satisfactory, such compositions should be stable,non-toxic, and blendable with other ingredients to provide its ownunique flavor and aroma nuance without detracting from theco-ingredients. Preferably, such compositions should be naturallyoccurring or present in natural foodstuffs (although unrecognized as aflavor component thereof) so that its ingestible safety can be readilyrecognized. Additionally, these materials should be capable of beingsynthesized in a simple and economic manner.

While the various a-ketothiols of this invention are old compounds whichsynthesis has been described in the literature (see, e.g. Chem.Abstracts, 61: l859d (1964), no one has previously recognized ordiscovered that these compounds are useful flavoring materials. The art(Badings, J. Dairy Science, 50, No. 9, pp. 1,347 et seq. (1967)) hasnoted that B-ketothiols, namely 2-mercapto-2-methyl-pentan-4-one, is thecause of an off-flavor in cheese.

It has now been found that the flavor of foodstuff can be altered byadding thereto a small but effective amount of at least one a-ketothiolhaving the formula wherein R, is methyl or ethyl and R and R arehydrogen, methyl or ethyl. it is generally preferred that R be hydrogenand R be methyl. The invention also contemplates flavoring compositioncontaining such a-ketothiols.

Suitable a-ketothiols include 2-mercapto-3-pentanone2-mercapto-3-butanone 2-mercapto-2-methyl-3-butanone2-mercapto-2-methyl-3-pentanone 2-mercapto-2-ethyl-3-butanone2-mercapto-2-ethyl-3-pentanone The a-ketothiols of this invention havinga strong aroma and taste agreeably resembling that of meat. The compound2-mercapto-3-butanone has been found by applicants in the volatilecomponents of a meat flavor composition obtained by heating a proteinhydrolysate, cysteine, and thiamine.

Such a a-ketothiols are accordingly useful in flavoring compositions.Such a composition is taken to mean one which contributes a part of theoverall flavor impression by supplementing or fortifying a natural orartifical flavor in a material, as well as one which suppliessubstantially all of the flavor and/or aroma character to a consumablearticle. The a-ketothiols of this invention are particularly suitablefor rounding out and improving the character of meat flavorcompositions.

When the a-ketothiols according to this invention are used in aflavoring composition, they can be combined with conventional flavoringmaterials or adjuvants. Such co-ingredients or flavoring adjuvants arewell known in the art for such use and have been extensively describedin the literature. Apart from the requirement that any such adjuvantmaterial be ingestibly acceptable, and thus non-toxic or otherwisenon-deleterious, conventional materials can be used and broadly includeother flavor materials, vehicles, stabilizers, thickeners, surfaceactive agents, conditioners, and flavor intensifiers.

Such conventional flavoring materials include saturated and unsatruatedamino and fatty acids, alcohols, including primary and secondaryalcohols; esters; carbonyl compounds including ketones and aldehydes;lactones; other cyclic organic materials including benzene derivatives,alicyclics, heterocyclics such as furans, pyridines, pyrazines and thelike; sulfurcontaining materials including thiols, sulfides, disulfidesand the like; proteins, lipids; carbohydrates; socalled flavorpotentiators such as monosodium glutamate, guanylates, and inosinates;natural flavoring materials such as cocoa, vanilla, and caramel;essential oils and extracts such as anise oil, clove oil and the like;artificial flavoring materials such as vanillin; and the like.Particularly suitable flavoring agent adjuvants are protein hydrolysate,cystein, thiamine, and reaction products of one or more of them.

Stabilizers include preservatives such as sodium chloride, and the like,antioxidants such as calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate andthe like, sequestrants such as citric acid, EDTA, phosphates, and thelike.

Thickeners include carriers, binders, protective colloids, suspendingagents-emulsifiers and the like, such as agar-agar, carrageenan,cellulose and cellulose derivatives such as carboxymethyl cellulose andmethyl cellulose, natural and synthetic gums such as gum arabic, gumtragacanth and the like, and otherproteinaceous materials, lipids,carbohydrates, starches and pectins.

Surface active agents include emulsifying agents such as monoand/ordiglycerides of fatty acids such as caproic acid, caprylic acid,palmitic acid, myristic acid, oleic acid, and the like, lecithin,defoaming and flavordispersing agents such as sorbitan monostearate,potassium stearate, hydrogenated tallow alcohol, and the like.

Conditioners include compounds such as bleaching and maturing agentssuch as benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents such as sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants such as carminic acid, cochineal, turmeric, curcumin, approvedfood and drug dyes, and the like; firming agents such as aluminum sodiumsulfate, calcium chloride and calcium gluconate; texturizers; anticakingagents such as aluminum calcium sulfate and tribasic calcium phosphate;enzymes; yeast foods such as calcium lactate and calcium sulfate;nutrient supplements such as iron salts, such as ferric phosphate,ferric pyrophosphate, ferrous gluconate and the like, riboflavin,vitamins, zinc sources such as zinc chloride, zinc sulfate, and thelike.

The a-ketothiols, or the compositions incorporating them, as mentionedabove, can be combined with one or more vehicles or carriers for addingthem to the particular product. Vehicles can be edible or otherwisesuitable materials such as ethyl alcohol, propylene glycol, water, andthe like. Carriers include materials such as gum arabic, carrageenan,other gums, and the like. The a-ketothiols can be incorporated with thecarriers by conventional means such as spray-drying, drumdrying, and thelike. Such carriers can also include materials for coacervating thea-ketothiols (and other flavoring ingredients, as present) to provideencapsulated products. When the carrier is an emulsion, the flavoringcomposition can also contain emulsifiers such as mono-and diglyceridesof fatty acids and the like. With these carriers or vehicles, thedesired physical form of the composition can be prepared.

It will be understood by those skilled in the art that the a-ketothiolscan be added to the materials to be flavored at any convenient point inthe production of the finished product. Thus, when the a-ketothiols areused to alter the flavor of a foodstuff, they can be added in theoriginal mixture, dough, emulsion, batter, or the like prior to anycooking or heating operation. Alternatively, they can be added at alater stage of processing if volatilization losses would be excessiveduring the earlier processing.

The quantity of a-ketothiols or mixtures thereof utilized should besufficient to impart the desired flavor characteristic to the productbut on the other hand, the use of an excessive amount of thea-ketothiols is not only wasteful and uneconomical but in some instancestoo large a quantity may unbalance the flavor or other organolepticproperty of the product consumed. The quantity used will vary dependingupon the ultimate foodstuff, or other consumable product; the amount andtype of flavor initially present in the product; the further process ortreatment steps to which the product will be subjected; regional andother preference factors; the type of storage, if any, to which theproduct will be subjected; and the preconsumption treatment, such asbaking, frying, and so on, given to the product by the ultimateconsumer. Accordingly, the terminology effective amount" and sufficientamount is understood in the context of the present invention to bequantitatively adequate to alter the flavor of the foodstuff.

It is preferred that the ultimate compositions contain from about 0.001part per million (ppm) to about ppm of a-ketothiols. More particularly,in meat or simulated meat-like food compositions it is desirable to usefrom about 0.003 to about 0.1 ppm for enhancing flavors and in certainpreferred embodiments of the invention, from about 0.01 to about 10 ppmof the a-ketothiols are included to add positive flavors to the finishedproduct.

All parts, proportions, percentages, and ratios herein are by weightunless otherwise indicated.

The amount of a-ketothiols to be utilized in flavoring composition canbe varied over a wide range depending upon the particular quality to beadded to the foodstuff or other consumable material. Thus, amounts ofone or more a-ketothiols according to the present invention from about0.1 percent up to or percent can be incorporated in such compositions.It is generally found to be desirable to include from about 0.5 to about25 percent of the a-ketothiols in such compositions.

It will be appreciated from the present disclosure that the a-ketothiolsand mixtures thereof according to the present invention can be used toalter, vary fortify, modify, enhance, or otherwise improve the flavor ofa wide variety of materials which are ingested, consumed, or otherwiseorganoleptically sensed.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE 1 The following are homogeneously admixed at 25C:

INGREDIENTS Vegetable shortening Salt Glutamic acid L-CysteineHydrochloride I Glycine B-Alanine Taurine Mixture of di-sodium inosinateand di-sodium guanylate 2-Mercapto-3-pentanone PARTS 622.7 321.7

This mixture is heated to 300 F for 30 seconds. After cooling to F, 0.12part of diacetyl and 0.10 part of hexanal are added. The resultingmixture has an excellent chicken aroma.

EXAMPLE II The following materials are homogeneously mixed at 25 C:

INGREDIENTS Vegetable shortening Salt Glutamic acid 5 L-Cysteinehydrochloride l0. Glycine 5. fl-Alanine l Taurine 20. Mixture ofdi-sodium inosinate and di-sodium guanylate 3 The mixture is heated at300 F for 30 seconds. After cooling to 100 F, 0.12 part of diacetyl and0.10 part of hexanal are added. After aging the resulting mixture forthree hours 0.] part of 2-mercapto-3-butanone is added.

The resulting mixture is aged for hours to provide a material having anexcellent chicken aroma.

EXAMPLE lV INGREDIENTS PARTS Vegetable shortening 622.7 Salt 321.7Glulamic acid 5.1 L-Cysteine hydrochloride 10.3 B-Alanine 1.3 Taurine20.0 Mixture of di-sodium inosinate and di-sodium guanylate 3.32-Mercapto-3-butanone 0.05 0.05

2-Mercapto-3-pentanone The resulting mixture has an excellent chickenaroma.

EXAMPLEV The following ingredients are homogeneously mixed at 25 C:

INGREDIENTS PARTS Vegetable shortening 622.7 Salt 321.7 Glutamic acid5.1 L-Cysteine hydrochloride 10.3 Glycine 5.l fl-Alanine 1.3 Taurine20.0 Mixture of di-sodium inosinate and di-sodium guanylate The mixtureis heated to 300 F for 30 seconds. After cooling to 100 F, 0.12 part ofdiacetyl, 0.10 part of hexanal. and 0.1 part of 2-mercapto-3-butanoneare added.

The resulting mixture has an excellent chicken aroma.

EXAMPLE V1 The following ingredients are homogeneously mixed at 25 C:

INGREDIENTS Vegetable shortening Salt Glutamic acid 5 L-Cysteinehydrochloride l0. Glycine 5. fi-Alanine 1 Taurine 20. Mixture ofdi-sodium inosinate and di-sodium guanylate 2 The mixture is heated to300 F for 60 seconds. After cooling to 100 F, 0.12 part of diacetyl and0.10 part of hexanal are added. After aging the mixture for a period of3 hours at a temperature of 65 F, 0.05 2-mercapto-3-butanone are added.The resulting mixture is then aged for 10 hours to yield a compositionhaving an excellent chicken aroma and flavor.

a. Cysteine hydrochloride in the amount of 8.8 g is refluxed at 215 Funder atmospheric pressure for 4 hours with a mixture of 309 g ofhydrolyzed vegetable protein, 8.8 g thiamine l-lcl, and 674 g of water.Subsequent to the reflux, the mixture is cooled and 0.05 g2-mercapto-3-pentanone is added and intimately admixed with thecomposition. The mixture has an excellent beef flavor.

b. The beef flavor produced in Example VII (a) is added to:

1. a commercial dry type pet food; 2. a semi-moist type pet food; and 3.wet or canned pet food.

When so added at levels of 0.5 percent, 1 percent, 1.5 percent, 2percent, 2.5 percent and 3 percent (by weight of foodstuff) highlypalatable pet foods are obtained.

EXAMPLE VIII The composition prepared in Example I is dissolved inpropylene glycol to provide a 0.1 percent solution. This solution in theamount of 0.966 g is added to 7.3 g of a soup base consisting of:

INGREDIENTS PARTS Fine ground sodium chloride 35.62 Hydrolyzed vegetableprotein 27.40 Monosodium glutamate 17.81 Sucrose 10.96 Beef fat 5.48Sethness caramel color 2.73

(powder B&C)

The composition of Example 11 (0.005 g) when added to the above soupbase also provides a soup having good meat flavor.

EXAMPLE 1X The composition prepared in Example V1 is dissolved inpropylene glycol to provide a 0.1 percent solution. This solution in theamount of 0.966 g is added to 7.3 g of a soup base consisting of:

INGREDIENTS PARTS Fine ground sodium chloride 35.62 Hydrolyzed vegetableprotein 27.40 (Maggi 48E) Monosodium glutamate 17.81 Sucrose 10.96 Beeffat 5.48 Sethness caramel color 2.73

(powder B&C)

may be obtained by reacting a protein hydrolysate, cysteine andthiamine, having the formula Raul,

wherein R; is methyl or ethyl, 5535M R are hydrogen, methyl or ethyl,and an auxiliary flavoring adjuvant.

6. A flavoring composition as defined in claim 5 wherein R is hydrogenand R, is methyl.

7. A flavoring composition as defined in claim 5 wherein R is methyl, Ris methyl and R is hydrogen.

8. A flavoring composition as defined in claim 5 wherein R is ethyl, Ris methyl, and R is hydrogen. l l i

2. A process as claimed in claim 1 wherein R3 is hydrogen and R2 ismethyl.
 3. A process as claimed in claim 1 wherein R1 is methyl, R2 ismethyl and R3 is hydrogen
 4. A process as claimed in claim 1 wherein R1is ethyl, R2 is methyl and R3 is hydrogen.
 5. A flavoring compositionadapted to alter the meat or poultry flavor of a foodstuff containing asthe Essential ingredient an Alpha -ketothiol, other than that which maybe obtained by reacting a protein hydrolysate, cysteine and thiamine,having the formula
 6. A flavoring composition as defined in claim 5wherein R3 is hydrogen and R2 is methyl.
 7. A flavoring composition asdefined in claim 5 wherein R1 is methyl, R2 is methyl and R3 ishydrogen.
 8. A flavoring composition as defined in claim 5 wherein R1 isethyl, R2 is methyl, and R3 is hydrogen.